New azo dyestuffs



Patented Mar. 29, 1932 Units .srArEs WINFRID Huntsman AND MAX HABDTMANN, onWinsnoRr on-THn-aiimn; RUDOLF V KN'OCHE, or LEVERKUSEN-ON-THE-RI-IINE, AND rennan STI'TSSER, OF co oGNEf- DEUTZ, GERMANY, ASSIGNORS TO GENERAL ANlLINE OR mg? NEW YORK.

N. Y., .A-CORPORATION OF DELA ARE,

' l 7 N W] zo nYnsmurrs The present invention relates to new disaz jo dyestuffs; more particularly it relates to dyestufi's of the probable general formula:

wherein X stands for a residueof the group consisting of; diphenyl, diphenylureaand Rs stand for sulfonated aromatic nuclei of the benzene and naphthalene series which may be further substituted by O-alkyl or halogen. I Our new dyestufls are 'obtalnahle by coupling two molecules of a sulfonic'acid of an aceto acet arylide'ot the general formula relim. R

wherein R stands for a sulfonated aromatic nucleus of the benzene or naphthalene series '1 which may be otherwise 'substituted with a 35 hibit, in spite of the presence of more than one sulfonic acid group, very good solubility properties besides an excellent affinity for vegetable fibre, particularly cotton and artificial silk. It is to be understood that tetrazo 40 compounds of higher molecular amines as for instance 4,4!-tetrazo-1.l-diphenyl-.3,3-dicarboxylio acid or the tetrazo compound of 4.4- diamino-Ll-diphenyl urea. -dicarboxylic acid etc. are included in the-invention. i 7 Obviously thedisazo dyestu-lis obtainable low, cotton greenish-yellow shades.

. No Drawing. Application filed February 10, 1928, Serial No; 253,522, and in Germany February 21, 1927.

from compounds of the latter type canbe produced indirectly instead ofStartingfrom the tetrazo compounds of the'diamines, have ingthe carboxylic groupsin the .ortho-p'o'si tion to the amino groups'and coupling vwith i the sulfonicacids of the aceto'acet arylidgs; 3 viz. bythe subsequent linking up of the two monoazo dyestuffs obtainable from thediazo 1 compound of an amine containing a carboX- yllc group in the ortho position to the ammo gr oup and a sulfonlc acid of an aceto acet ary id The dyestuffs hus obtained are greenish yellowto orange compounds, easily soluble in 7 water, difficultly soluble in the usual organic 3 Theil olution in sulfuric'ajcid is solvents. yellow.

on the vegetable fibre, particularly on cotton and artificial silk, clear yellow, orange and On dyeing-these substantive azojdyestliffs brown shades are obtainable possessing a satisfactory fastness to light.-When treating the dyeings on the fibre in'the customary manner. with metal salts, dyeings very fast to light" and especially fast to washing are obtained.

v 3 The following examples will illustrate our invention withoutlimiting it thereto Example J. The 'tetrazo compound from 330 --parts-by weight-ofxlr-diamino diphenyl urea-8.3-dicarboxylic acid,prepared with the customary precautions, isadded to an aqueous solution, rendered alkaline with sodium carbonate, of 690. parts by weight of the sodium sulfonateofaceto a-ce't-orthoechloranilide.

When thetcoupling .is complete, the yellow dy'estuif is salted tout and .is obtained in the crystalline form. It :dyes viscosepure yel When the dyeings on cottonfare subsequently treat- .ed'with cop-per salts,-very fast yellow shades are obtained. V o .7

'Emample 2. Tl1e tetrazo compound from 272 parts-by weight of hl'e-diamino diphenyl- -'3.3'-dicarboxylic acid is added to an; aqueous aqueous solution,

solution, rendered alkaline with sodium carbonate, of 938 parts by weight of the sodium disulfonate of acetoacet-l-naphthylamide. The working up is effected as usual. The dyestuff dyes viscose orange yellow, cotton yellow shades. hen the dyeings on cotton are subsequently treated with copper salts, brownish-yellow shades are obtained.

Example 3.The tetrazo compound from 330 parts by weight of 4.4-diamino diphenyl urea-3.3-dicarboxylic acid, prepared with the customary precautions, is added to an rendered alkaline with sodium carbonate, of 574 parts by weight of the sulfonic acid of aceto-acet-ortho-anisidide (In-p. 143 C.) When the coupling is complete, the yellow dyestuif having in the free state the following formula:

soar HOaS I HN which is immediately changed into another product, the constitution of which is as yet unknown.

Example 4.182 parts by weight of 5- nitro-2-amino-benzoic acid are diazotized and coupled with an aqueous solution, rendered alkaline with sodium carbonate, of 287 parts by weight of the sulfonic acid of aceto acet-ortho anisidide (m.-p.-143 C.) The nitro group is then reduced with a slight excess of crystallized sodium sulfide and phosgene is then used to transform the monoazo compound into the symmetricalurea in the customary manner. The dyestuif is identical with that of Example 3.

If instead of phosgene, thiophosgene or carbon-disulfide are used, the corresponding gOHa 7 yellow,

. HIT-R. wherein X stands for a residue of thegroup consisting'of diphenyl, diphenylurea and diphenylthiourea, each of the phenyl nuclei of the residue bearing a carboxylic acid group halogen, said dyestuffs being greenish-yellow to orange powders easily soluble in water, soluble in strong sulfuric acid with a yellow coloration, dyeing the vegetable fibre, particularly cotton and artificial silk clear orange and brown shades.

2. As a new. product the dyestutf of the probable formula COOH O-N=N-$H so,H

(to-NH 00-011: H N=N-trr SOaH tam 0011 7 said dyestuffs being a reddish yiellow powder easily soluble in water, soluble in strong sulfuric acid with a yellow coloration, exhibiting very good solubility properties besides an excellent aliinity for vegetable fiber, particularly cotton and artificial silk, dyeing viscose and cotton beautiful golden yellow shades the latter changing to a clear yellow of good fastness on subsequent treatment with copper salts, and yielding ontreatment with stannous chloride in acid solution 1 molecule of 4.4-diamino-diphenyl-ureaunkn 3.3'-dicarboxylic acid and two molecules of a compound of the probable formula HzN-JJH SOiH swag which is immediately changed into another product the constitution of which is as yet own. 3. As new products the disazo dyestuffs of the probable general formula:

0H8 GOOH coon 7 =0 (i=0- H(ilN=N NH-G-NH LEN-(in =0 v =0 HN-R I our hands.

WINFRID HENTRICH. MAX HARDTMANN. 'RUDOLF KNOOHE.

RICHARD STUSSER. i

Err-R. 

